Highly radiation-sensitive telomerized polyamides



3,483,105 Patented Dec. 9, 1969 P ICC United States Patent containing 21() carbon atoms; R represents hydrogen or 3,483,105 CH R"" represents hydrogen or an aliphatic hydro- HIGHLY RADIATION-SENSETIVE TELOMERIZED b OLYAMIDES car on radical of l 18 carbon atoms, and X represents Gaetano F. DAlelio. South Bend, Ind., assignor, by mesne hydrogen or an acyl group of the formula R The assignments, to PPG Industries, Inc., a corporation of Pennsylvania radical derived from an unsaturated aliphatic dicarboxylic N0 Drawing Filed May 18, 1966, Sen 1, acid such as maleic, fumaric, itaconic, citraconic, mesa- Int. Cl. 1301i 1/10; C0811 l/00; (308E 1/16 Come,

U.S. Cl. 204159.15 24 Claims These highly radiation-sensitive telomerized polyamides are prepared from appropriate acrylyl derivatives such as the glycidyl esters,

ABSTRACT OF THE DISCLOSURE The preparation of highly radiation-sensitive telomerized diacrylyl polyamides whereby said polyamides are treated by subjecting same to high energy ionizing radia- 0 tion so as to produce three-dimensional crosslinked, iny reaction With carboxyl terminated Unsaturated soluble infusible polymers at relatively low doses of ioniz- Phetie p y In these eases, the y y aefylate ing radiation. which is a derivative of the trihydric glycerine yields linear ester-amides containing one free unreacted hydroxy'l group.

This invention in general deals with radiation-sensitive The carboxyl terminated unsaturated aliphatic polypolymers. Particularly it concerns viscous or solid, soluble, amides are derived y the reaction of the above-menfusible, relatively low molecular Weight oly r r f r d tioned unsaturated aliphatic dicarboxylic acids with a dito as oligomers, which, when subjected to ionizing radiain an alkanolamine, a mixture of a diamine and 21 tion become insoluble and infusible. More specifically, it 25 g y miXture Of an alkaholemifie and a y These deals with telomerized polyamides which, on irradiation, i n a m n s and gIYC I an be represent d convert to three-dimensional crosslinked, insoluble, iny the formulas 2 z, z a HOR'OH fusible polymers at relatively low doses of ionizing irp i ely While e group is preferred as the radiation. connecting amide group, it is considered equivalent for The telomerized polyamides of this invention are linear most p p ses f t is inventi n to use -NR'- With R polyamides which are derived from the condensation of as defin d ab ve. The corresponding alkylene imines,

a glycidyl acrylate with a linear condensation polymer -I of unsaturated aliphatic, including cycloaliphatic polycarboxylic acids with saturated or unsaturated aliphatic, including cycloaliphatic, diamines, or aminoalcohols. can, when available, also be used, wherein R" is H or These telomerized polyamides have as end groups the an alkyl group having l10 carbon atoms.

highly radiation-sensitive acryloxy group having the In view of the reactivity of amines with the unsaturaformula tion in acrylic acid and in the unsaturated dicarboxylic 40 acid, precautions should be taken to avoid or to minimize this side reaction. The addition of amines to ethylenic I GH2=CTCOOCH2(|JHCH2T or unsaturated groups is retarded by suspending the 0X reagents in a hydrocarbon solvent such as Xylene, ben- The term polyamides is used generically herein to Zehe, e p eyclohexahe, The Y- inelude amid st r copolymers as ll as polymers i drocarbon is advantageously removed when 1t1s no longer which substantially all the condensation groups are amide needed for thls P p The amlne flddltlOIl t0 the 11!!- groups, saturated group can also be avoided by using acid chlo- Accordingly thes radiation-sensitive t l i d polyrides of the dicarboxylic acids for reaction with amines amides have the formula to form the polyamides. CH2=CCOOCHflEHCHzOOCRCOlAR'AOCRCOhOCIhfiJHCHzOOCC=CH2 B OX OX R wherein n represents a numerical value of 1 to 14; A rep- Thus a dicarboxyl terminated unsaturated aliphatic resents O or NH but t l t one A group per polyamide can be reacted with glycidyl acrylate to promolecule represents NH-, and preferably at least duce linear hydroxyl substituted radiation sensitlve polyof the A groups represents NH; R represents a divaamides, thus R RI! CHz=( JC O O CH2CHOH2O O C RC OINHR'NHO C RC 01,10 CH2CHCH2O O CC=OH2 OH OH Eq.(1 lent aliphatic (including cycloaliphatic) hydrocarbon When an alkanolamine, or a mixture of a diamine and radical having 2-10 carbon atoms with at least 75% of either an alkanolamine or a glycol, is used in place of said R groups per polyamide molecule being unsaturated; the diamine in the above reaction the product is similar R represents a divalent aliphatic hydrocarbon radical to that of Equation 1 except some of the NH radicals (saturated or unsaturated and including cycloaliphatic) have been replaced by O radicals.

radical OCRCO can be defined as the dicarboxylic,

3 4 Telemerized polyamides with a greater number of re- In the above formulas the derivatives of the glycidyl peating segments, and therefore of higher molecular acrylate component are represented by the structure weight than the simplest polyamides, are prepared by ,=c cooH,oHoH2- increasing the ratio of the n moles of diamine, etc. and H the n+1 moles of dicarboxylic acid to the 2 moles of X glycidyl acrylate to maintain the molar ratio of diamine, 5 However It Is recognlzed that the exlrane r g of the yetc.:diacid:glycidyl acrylate at n:(n+l) :2. Thus it may cidyl group y react so that the s n structure,

be seen that the simplest polyamide is obtained with one UH2=C COOCH2CH mole of diamine; two moles of diacid and two moles of t J OX glycidyl acrylate. When the value of n is increased for the 2 diamine to 2, the value for the diacid becomes 3 and that may be formed. It is intended that both of these isomeric for the acrylic function remains constant at 2. structures are covered by the various formulas given The linear polyamides can be prepared by various types herein.

of standard reactions used in preparing amides starting As previously pointed out, the use of the hydrocarbon with unsaturated acids or their anhydrides or acid halides suspension medium to eliminate or retard amine addition and diamines, etc., or alkylene imines. The conditions to the unsaturated group during amidification can be used are those appropriate for the normal reactions of avoided by using the unsaturated dicarboxylic acid in its amines with unsaturated acids, anhydrides and acid hahalide form, for example:

(n+1) R COCD2 n R(NH2)2 ClOCRICONHRNHOCRjcCOCl I 20112 CHCOO CH CHCHzOH OH H (Eq. 3) lides to form amides, and also those normally used for Depending on the nature of R, R and R" the viscosity the reaction of the glycidyl group with acids. of these telomerized polyamides increases from about 300 The hydroxy substituted acrylyl terminated polymer to 50,000 centistokes at C. as the value of It increases amides as represented broadly by the above 'formulas from 1 to 14. Also depending on the values of n R and have specific and improved utility especially when polym- Rf, the molecular weight of these telomerized amides erized in the presenee Of Cellulose such as wood, p p will vary from about 275 for the lowest one at a value of fibers, fiber board, in the form of a Coating, P n=1 to about 8800 for 11 equal to 14 when the diacid is 1131111 or bonding agent The PresflnCe of the alcoholic Y' decenedicarboxylic acid and the diarnine is dodecanedidroxyl causes improved wetting of cellulose and because of hydrogen bonding of the hydroxyl group with the cellulose, yields improved adhesion compared to the unsubstituted oligomeric polyamides.

In those cases where the presence of these hydroxyl groups is not desired or is deterimental to such properties 40 as dielectric constant or power factor, the hydroxyl groups or he aclichlonde form of the acld In order 9 avoid can be converted to ester groups by acylation with aliaddmol} to the imsaturated glioupst and phatic acids, wherein n is H or an aliphatic portions to give terminal carboxylic groups. Then. the

amine.

In cases where it is desirable to have predominately amide mixtures in the polymer, the center portion of the polymer can be made entirely by the reaction of a diamine with the dicarboxylic acid, using a hydrocarbon medium saturated or unsaturated hydrocarbon group containing prepafation f the telomerized Polymer can be cofnpleted 1 to 18 carbon atoms, such as formic, acetic, propionic, y 11S1 I1g glycldyl acrylate cases Where the trmmal butyric, acrylic, methacrylic, oleic, stearic acid, etc., or XY groups are free acld g p and 115mg Y Y their anhydrides forming a class of polyamides suitable in monoacrylate when the terrmnal carboxyhc groups are the practice of this invention, thus: acid chloride groups.

R RI! I CH2 CCOOCHZCHCHQOOCRC0[ARAOORCO],,OCH2?HCH OOOC=CH2 H OH If]! 2 R/IlICOOH $11! CH :CGOOCH2CHCHz0OC-RCO[ARAOCRCOhOCHzCHCHzOOCC=CH OCRIHI OOCRR (Eq. 2) The radiation sensitive oligomeric polymers of Equation As previously pointed out the use of the hydrocarbon 2 are particularly useful especially when admixed with medium for conducting the condensation reaction of the P Y as nylon, unsaturated Polymeric alkyd carboxylic acid and amine groups avoids addition of the esters such as polyethylene maleate, polyethylene fumarate, etc.

. Acrylation of the hydroxyl substituted telomerized polyamide of Equation 1 by means of an acrylic acid, or its acrylic anhydride or chloride produces a class of telomamine to the unsaturated groups. When the acid chloride or other halide is used, the halide has such a great affinity for the amine group that the amidification is effected in preference to any amine addition to the unsaturated erized radiation-sensitive polymers which, because of the r When an acid halidc used it is generally increased number of acrylyl groups, shows an even more slrable to use a hydrogen hallde'acccptol' Such as 3 improved response to ionizing radiation, thus tiary amine.

' CH2 CCOOCH2JHOH2OOCRCOIAR AOORCO]nOCH2CHCH2OOC=CHZ 2 (CHz=C-C0)z0 OH H R" C u 1 CH2=A 000CEZCHCH OOGRC lAR'AQORCOLrOCHZOHCHzOOCC=CH2 Typical examples of the various NH RNH diamines and amino or alcohol segments. It is because of this alithat can be used in synthesizing the telomerized polyphatic character that these telomerized polyamides are amides of this invention are ethylene diamine, tetramethylhighly responsive to ionizing radiation, and in fact, subene diamine, 2,3-diaminobutane, 1,4-diaminobutane, 1,4- stitution of any of the aliphatic polycarboxylic acids by diarnino-Z-ethylbutane, l,6-diaminohexane, 1,8-diamino aromatic carbo-xylic acids or substitution of the aliphatic octane, 2,10-diaminodecane, 1,4-diaminocyclohexane, 1,4- 5 amino or alcohol components by aromatic amino or alcobis-(aminomethyl)cyclohexane, 1,3-diaminocycloheptane, hol compounds, decreases the response to ionizing irradi- 2,2-diethylpropanediamine-l,3, 2,2-dimethylpropanediation to such a point that they are not economically amine-1,3, 3-methylpentanediamine-1,4, Z-diethylbutanefeasible.

diamine-1,3, 4,5-diarnino-nonane, pentamethylene di- As an example, the dimethacrylyl telomerized polyamine, heptamethylene diamine, nonamethylene diamine,

ethylene maleamide, a t OIIFC-C O[NHCH2CH2NHO O CH=CHC OhNHCH CH NHO CO=CH crosslinks at about 3 megarads, whereas the corresponding phthalyl derivative,

decamethylene diamine, diethylene triarnine, triethylene requires 16 megarads to make it insoluble and infusible.

tetraamine, propylene diamine, dipropylene diamine, 2- This difference is surprising particularly :because these ethylhexanediamine-l,3, 1,4-diamine diamino butene-2, telomerized amides all cure with radical initiators such as 1,4-diamino-cyclohexene-Z, 8-diamino-octene-4, etc. Al- With 1% benzoyl peroxide in about 90 to 95 seconds at kylene imines can also be used to give corresponding cli- 100 C., and with redox systems of cobalt acetate and amine derivatives, such as propylene imine, ethylene tertiary butyl hydroperoxide in three to three and oneirnine, 2,3-butylene imine, etc. While amines such as dihalf hours at room temperature. This difference is due ethylene triamine, etc., have an intermediate amino group apparently to the fact that aromatic ring compounds such between the terminal amine groups, they are considered as phenyl, naphthyl and the like are energy sinks for equivalent to the diamines listed above for the purpose irradiation. fthi i ti It will be noted too that the aliphatic hydrocarbon T i l examples f io lka ol in th t can structures in the polycarboxylic segments are unsaturated. be used in synthesizing telomerized polymeric amide- This is for the purpose of imparting rigidity to the irradiegters of this invention, are; ethanglamine, propanolaated products. While the unsaturation in the acrylyl mine, butanolamine, hexanolamines, decanolamines, etc., groups at the ends of tha telomerized diacfyl polyamides h as Z-arginocthanoL Z-a i M, 3- i is more easily available for crosslinking and insures more 14, 3-aminopyopanoL2 4 4 i b m 1 1, 3- iimmediate and more easily attained crosslinking, the unnobutanol-2, 4-aminopentanol-1, 6-aminohexanol-1, 7- saturation provided along the linear chain of the teloaminooctanol-Z, 9-aminodecanol-2, l0-aminodecanol-1, I- mailed polyamide y Virtue 0f the uration in the amino-8hydroxy-decene-5, 1-amino-4-hydroxy-butene-2, unsaturated dicarboxylic acid groups Permits a greater 1-an1ino-4-hydroxy-cyclohexene-Z, etc. number of crosslinkages in a polymer molecule and there- Some in i examples f the various by imparts a more rigid character to the resultant irradialcohols which can be used in synthesizing telomerized flied polyamidi polymeric amide-esters of this invention are ethylene The telomerized polyamides of this invention are parglycol, trimethylene glycol, tetramethylene glycol, 2,3- ticularly useful for blending with various types of polydihydroxybutane, 1,4-dihydroxybutane, 1,4-dihydroxy-2- amides, particularly those which are not easily crosslinked ethylbutane, 1,6-dihydroxyhexane, 1,8-dihydroxy-octane, by radiation or which require such a high degree of 2,10-dihydroxydecane, 1,4-dihydroxycyclohexane, l,4-di radiation for crosslinking as to be accompanied by decommethylolcyclohexane, 2,2-diethyl-propanediol-1,3, 2,2-diposition, degradation, or discoloration. Where the telomermethyl-propanediol-l,3, 3-methylpentanediol-1,4, 2,2-diized polyamide of this invention is blended with a polyethylbutanediol-1,3, 4,5-dihydroxynonane, pentamethyl- 5O amide substance such as a nylon or polycaprolactamide, ene glycol, heptamethylene glycol, nonamethylene glycol, the similarity in the structure of the polyamide of this decamethylene glycol, diethylene glycol, triethylene glycol, invention with the structure of the polyamide to which propylene glycol, dipropylene glycol, butene-2-diol-l,4, it is being added facilitates the blending and makes it 2,7-dihydroxy-n-hexene-4, 2,7-dihydroxy-2,7-dimethyl-nmore compatible therewith, resulting in less destruction hexene-4, 2-ethylhexanediol-l,3, etc. Alkylene oxides can 0f detfactioh from the Properties of the g nal P 3- also be used to give corresponding glycol derivatives, Iner. This permits a blending of a crosslinking agent of such as propylene oxide, ethylene oxide, 2,3-butylene improved compatibility and permits subsequent crosslink- Oxide em mg by radiation without any disruption of or detraction s ill ti examples f th various from the basic properties of the original polymer. Consequently, the improvements effected by crosslinking are HOOCRCO H not ofiset in any manner by the presence of incompatible acids which can be used in preparing the telomerized gFOHPS or groups Whlch are less itable or have properties polyam des of this invention are maleic, furnaric, 35 132; from those of the amlde groups of the base itaconic, citraconic, mesaconic, acetylene dicarboxylic, aconitic, alpha-methyl-itaconic, alpha-alpha-dimethyl-l,2- In of the fact that the Tadlafion dosage Previously tetrahydrophthalic, 1,3-tetrahydrophthalic, 1,4-tetrahydrorequired t0 effect y degree of crosslinking With most phthalic, trans-l,4-cyclohexenecarboxylic acids, etc. For R l/ was 50 g as to e accompanied by degradathe purpose of this invention, percent or more of the non of the Polymer, particularly With nylon, it is parrepeating unit segments derived from dicarboxylic acid ticularly important that blending Wi the telomerized should be of the unsaturated type. The remaining dicar- 70 polyamides of this invention Permits crosslinking of nylon boxylic acid se ments can be of the saturated aliphatic and other aliphatc Polymers to be eihicted at y low type, radiation dosages, as described more fully hereinafter,

It is most important to note that the various classes and thereby avoid degradation of the P y of telomerized polyamides of this invention contain ali- While the telomerized polyamides of this invention phatic hydrocarbon structures in their polycarboxylic acid have a particular utility with polyamide resins such as nylon and polycaprolactamide, they can be used with various other types of polymers, such as polyesters, both saturated and unsaturated, including maleic-ethylene glycol, phthalic-ethylene glycol, polyvinylacetate, methylmethacrylate, polyvinylchloride types, etc.

Where these telomerized polyamides are to be used with polyester types of resins, it is often desirable that the mixed amide-ester type of crosslinking agents of this invention be used. Likewise, when mixtures of polyamide and polyester resins are being blended for subsequent radi ation, it is desirable to use the mixed types of amideesters of this invention.

The term irradiation, as used herein, means high energy radiation and/ or the secondary energies resulting from conversion of this electron or other particle energy to neutron or gamma radiation, said energies being at least equivalent to about 100,000 electron volts. While various types of irradiation are suitable for this purpose, such as X-ray and gamma and beta rays, the radiation produced by accelerated high energy electrons has been found to be very conveniently and economically applicable and to give very satisfactory results. However, regardless of the type of irradiation and the type of equipment used for its generation or application, the use thereof in the practice of the invention as described herein is contemplated as falling within the scope of this invention so long as the ionization radiation is equivalent to about 100,000 electron volts.

While there is no upper limit to the electron energy that can be so applied advantageously, the effects desired in the practice of this invention can be accomplished with out having to go above about 20,000,000 electron volts. Generally, the higher the electron energy used, the greater is the depth of penetration into the massive structure of the materials to be treated, and the shorter is the time of exposure required to accomplish the desired result. For other types of irradiation, such as gamma and X-rays, energy systems equivalent to the above range of electron volts are desirable.

It is intended that the term irradiation include what has been referred to in the prior art as ionizing radiation which has been defined as radiation possessing an energy at least sufiicient to produce ions or to break chemical bonds thus includes also radiations such as ionizing particle radiation as well as radiations of the type termed ionizing electromagnetic radiation.

The term ionizing particle radiation has been used to designate the emission of electrons or highly accelerated nuclear particles such as protons, neutrons, alpha-pan ticles, deuterons, beta-particles, or their analogs, directed in such a way that the particle is projected into the mass to be irradiated. Charged particles can be accelerated by the aid of voltage gradients by such devices as accelerators with resonance chambers, Van de Graaff generators, betatrons, synchrotons, cyclotrons, etc. Neutron radiation can be produced by bombarding a selected light metal such as beryllium with positive particles of high energy. Particle radiations can also be obtained by the use of an atomic pile, radioactive isotopes or other natural or synthetic radioactive materials.

Ionizing electromagnetic irradiation is produced when a metallic target, such as tungsten, is bombarded with electrons of suitable energy. This energy is conferred to the electrons by potential accelerators of over 0.1 million electron volts (mev.). In addition to radiations of this type, commonly called X-ray, an ionizing electromagnetic radiation suitable for the practice of this invention can be obtained by means of a nuclear reactor (pile) or by the use of natural or synthetic radioactive material, for example, Cobalt 60.

Various types of high power electron linear accelerators are commercially available, for example, the ARCO type travelling wave accelerator, model Mark I, operating at 3 to 10 million electron volts, such as supplied by High Voltage Engineering Corporation, Burlington, Massachu- 8 setts, or other types of accelerators as described in United tates Patent No. 2,763,609 and in British Patent 762,953 are satisfactory for the practice of this invention.

In the following examples, the radiation doses are reported in megarads, which represent 1,000,000 rads. A rad is defined as the unit of absorbed dose and is equal to ergs per gram.

Many monomers as well as polymers have been subjected to ionizing radiation to convert them to improved or modified products. However, irradiation processes have been primarily of scientific interest, and very little use of such irradiated polymer processes have been made industrially. This is primarily due to economic factors because of the cost of the ionizing radiation delivered to the system to be treated. For example, the well-known lowcost polyester systems which consist of a mixture of about equal parts by weight of styrene monomer and an unsaturated alkyl resin prepared from maleic or fumaric anhydride, phthalic anhydride and ethylene glycol or diethylene glycol can be more economically polymerized by free radical initiators than by ionizing radiation which requires about 25 to 40 megarads, depending on the formulation.

Such systems can be improved somewhat, however, by elimination of phthalic anhydride in the formulation of the polyester and substituting the higher cost monomeric acrylic esters for the styrene. Even in such systems, the economic factors are unfavorable not only because of the much higher cost of the mixture but because of the high volatility of the acrylic or methacrylic esters used. Even in such cases the irradiation dose required is of the order of 18 to 20 megarads and the systems are highly inhibited by oxygen. The addition of substances such as acetone or methyl ethyl ketone can reduce the required dose to 9 to 12 megarads. Even then the products possess the undesirable odor of unpolymerized acrylic monomer.

In contrast, by the use of the acrylyl telomerized polyesters used in the practice of this invention and described hereinabove, crosslinked, insoluble, infusible polymers can be prepared readily by subjecting the polyesters to ioniz ing radiation in doses of less than 10 megarads and in some cases to doses of 0.5 magarad or less, generally preferably at least about 1 megarad. Irradiation dosages in this range are economical.

Furthermore, the acrylyl components in these telomerized polyamides are located at the ends of the polyamide chains where they can more efiectively crosslink. More important, the acrylyl components comprise a minor portion of the composition, and are particularly economical when the value of n in these telomerized polyamides as at least 2. In addition, because the molecular Weight of the telomerized polyamide is much higher than a corresponding simple monomer such as methyl methacrylate or ethyl acrylate, it can function in a single molecule both as monomer and as polymer.

This property of crosslinking at economical radiation doses is maintained when these telomerized polyamides are admixed with polyamide resins, such as nylon, or with unsaturated alkyd resins alone or in the presence of other polymers provided the polyamide resin, unsaturated alkyd resin and other polymers are of the nonaromatic type, that is, they are free of aromatic rings which act as energy sinks and retard the crosslinking reaction. One of the advantages of these diacrylyl polyamides is their compatibility with various types of resins particularly polyamide or alkyd types.

A few illustrative examples of suitable polymers which may be dissolved in or mixed with the telomerized polyamides of this invention along with the unsaturated alkyd resins are the non-aromatic type polymers such as nylon 66 (polyhexamethylene adipamide), polycaprolactam, polyvinyl acetate, polyethyl acrylate, polymethyl methacrylate, cellulose acetate, cellubutyrate, ethyl cellulose, polyethylene adipate, polyethylene azeleate, polydccamethylene succinate, polydecamethylene sebacate,

etc. The lower telomerized polyamides are also compatible with polyvinyl chloride particularly upon the application of moderate heat.

The telomerized polyamides of this invention are particularly useful as coating compositions on all types of substrates, including cellulose in its various forms, such as paper, wood, paper board, wood board, wood pulp, regenerated cellulose in film or fiber form, laminates of various types including those prepared from fibrous fillers bonded with urea, melamine, epoxy and polyester resins, plaster board, concrete in its various forms such as slabs, blocks and the like. They may also be used as impregnants for porous bodies such as the compositions hereinabove named, as well as for synthetic and natural sponges, etc. Particularly do they find use as bonding agents and adhesives for solid, porous and foamed bodies. They can be used alone or admixed with each other or with other copolymerizable monomers, unsaturated or saturated polymers, in the absence or presence of dyes, pigments, plasticizers. For coating, impregnating or adhesive compositions Where the presence of small amounts of solvent in the cured composition is not objectionable they can be mixed with volatile or non-volatile solvents of a non-aromatic nature best suited to the particular application. The products resulting from th irradiation of the telomerized polyamides of this invention can vary from soft flexible bodies too hard rigid masses.

The telomerized radiation-sensitive polyamides of this invention are particularly useful in the preparation of copolymers with unsaturated alkyd resins. In carrying this portion of the invention into effect, an esterification product of a polyhydric alcohol and an alpha, beta, unsaturated polycarboxylic acid is first prepared in accordance with techniques now well known to those skilled in the alkyd resin art.

Any aliphatic polyhydric alcohol containing at least two esterifiable aliphatic hydroxy groups, or mixtures of such alcohols, can be used in preparing the unsaturated alkyd resins. Examples of such polyhydric alcohols are ethylene glycol, di-, tri-, and tetra-ethylene glycols, thiodiglycol, glycerine, pentaerythritol, 1,4-dihydroxy-butene-2, dimethylol cyclohexane, dihydroxycyclohexane, etc. Any non-aromatic alpha-unsaturated, alpha, betapolycarboxylic acid, or mixtures of such acids, can be reacted with the polyhydric alcohol or alcohols to form the unsaturated alkyd resin. Examples of such polycarboxylic acids are maleic, fumaric, citraconic, mesaconic, acetylene dicarboxylic, aconitic, cyclohexene dicarboxylic, etc., itaconic and its homologues, as, for instance, alpha methyl itaconic acid, alpha, alpha-dimethyl itaconic acid, etc. Anhydrides of these polycarboxylic acids can also be employed.

In some cases, instead of using an unmodified, unsaturated alkyd resin, an unsaturated alkyd resin can be used which has been internally modified by replacing a part, say up to about 75 mole percent, of the unsaturated polycarboxylic acid with saturated aliphatic polycarboxylic acids, such as succinic, adipic, glutaric, pimelic, sebacic, azelaic, suberic, tricarballylic, etc.

Anhydrides of these acids, if available, can also be used. The term polycarboxylic acid as used generally herein is intended to include the anhydrides of the acids.

The esterification products of polyhydric alcohols with ethylenic polycarboxylic acids, or with aliphatic polycarboxylic acids, can be further modified by introducing as a reactant in the preparation of the alkyd resin, a monoesterifiable compound or compounds, more particularly a saturated or unsaturated normal or isomeric monohydric alcohol, or mixture thereof, a saturated or unsaturated monocarboxylic acid, or mixture thereof, or both such esterifiable monohydroxy organic compounds as well as by the use of hydroacids.

Examples of non-aromatic monohydric alcohols which can be used as modifiers of the alkyd resin are propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, octyl,

decyl, dodecyl, tetradecyl, cetyl, octadecyl, cyclohexyl, cyclopentyl, etc. The use of methyl and ethyl alcohol is not precluded, but in general these alcohols are less satisfactory because of their lower boiling points. As monobasic acids there can be used, for example, the unsubstituted saturated and unsaturated normal or isomeric monocarboxylic acids containing only one esterifiable group, such as acetic propionic, butyric to stearic, inclusive, hexahydrobenzoic, hexahydrotoluic, furoic acids, etc.

The monoesterifiable compounds can be introduced into the esterification before, during, or after the esterification of the polyhydric alcohol with the polycarboxylic acid under conditions that promote interesterification of the monoesterifiable compound with the incompletely esterified polyhydric alcohol-polycarboxylic acid product. That is, the monoesterifiable compound is introduced into the reaction mass before all of the acid groups of the polyhydric acid, or all of the alcohol groups of the polyhydric alcohol have been esterified.

The term unsaturated non-aromatic alkyd resins, as used generally herein and in the appended claims, is intended to include within its meaning both unmodified esterification products of a non-aromatic polyhydric alcohol with a non-aromatic alpha-unsaturated, alpha, betapolycarboXylic acid and esterification products of these components which have been modified, for example, as briefly described hereinabove. An alternate term is unsaturated aliphatic alkyd resins (including cycloaliphatic types To achieve copolymerization of the unsaturated alkyd resin with the telomerized polyesters of this invention, a solution or mixture of the unsaturated alkyd resin in the telomerized polyesters is first eflfected. Copolymerization of the components of the mixture is achieved rapidly and advantageously by ionizing radiation, such as by atomic radiation from a reactor, or from Cobalt 60, or by means of high energy electrons generated by an electron linear accelerator.

Typical examples of unsaturated alkyd resins are:

Alkyd resin A-Ethylene glycol itaconate Parts by wt. Ethylene glycol 23 Itaconic acid 52 The components are mixed and slowly heated in the course of one hour from room temperature to 190 C., in an inert nitrogen atmosphere, and held at this temperature for three to five hours.

Alkyd resin BEthylene glycol maleate Parts by wt. Ethylene glycol 31 Maleic anhydride 32 The compounds are mixed and heated as in the preparatron of alkyd resin A to C., and held at that temperature for four to six hours.

Alkyd resin CAcetic acid-modified diethylene glycol maleate Parts by wt. Diethylene glycol 106 Maleic anhydride 88 Acetic anhydride 10 The ingredients are mixed together and refluxed for one hour in an inert nitrogen atmosphere after which the reaction mixture is brought to C., which temperature is maintained for four to six hours.

It will be understood, of course, that this invention is not limited to the use of the specific unsaturated alkyd resins mentioned above and that a broad modification of the nature of the copolymer is possible by using other unsaturated aliphatic alkyd resins or mixtures of such resins. As illustrative examples of other unsaturated alkyd resins, the following esterification products can be used,

11 as illustrated in alkyd resins D to I. Aromatic alkyd resin I is included for comparison.

Alkyd resin: Components (parts) D Diethylene glycol (160). Maleic anhydride (147).

Di'ethylene glycol (106). Itaconic acid (130).

Glycerine (18.4). Itaconic acid (39.0).

Ethylene glycol (6.0). Maleic anhydride (19.6). Hydroxypropyl aerylate (26.0).

Ethylene glycol (20). Maleic anhydride (29.4). Succinic acid (3.3).

Diethylene glycol (30.6). Maleic anhydride (17.6). Itaconic acid (15.6).

Diethylene glycol (30.3). Maleic anhydride (13.2). Phthalic anhydride (21.7).

In many cases, instead of polymerizing a single telomerized polyester with a single unsaturated alkyd resin, mixtures can be used of two or more telomerized polyesters with a single unsaturated aliphatic alkyd resin, or a single telomerized polyester with two or more unsaturated aliphatic alkyd resins, or a mixture of two or more telomerized polyesters with two or more unsaturated aliphatic alkyd resins. In conjunction with the alkyd resins, comonomers can be used which are copolymerizable with the telomerized polyamide or with the unsaturated alkyd resins, or with both, for example, one or more telomerized polyamides can be used with one or more unsaturated aliphatic alkyd resins together with methyl methacrylate.

In addition to, or in lieu of the methyl methaerylate, other comonomers or mixture of eomonomers can be used, for example, the vinyl esters, that is vinylacetate, and the vinyl esters of saturated and unsaturated, and aliphatic, monobasic and polybasic acids, and more specifically the vinyl esters of the following acids: propionic, isobutyric, valeric, caprylic, capric, oleic, stearic, acrylic, methacrylic, crotonic, oxalic, malonic, succinic, glutaric, adipic, suberic, azelaic, maleic, fumaric, itaconic, mesaconic, hexahydrobenzoic, citric trimesic etc., as well as the corresponding allyl, methallyl, etc. esters of the aforementioned acids.

Other suitable comonomers are the acrylic and alkacrylic acids and their derivatives, such as their esters, amides and corresponding nitriles, for example, acrylic acid, methyl acrylate, butyl acrylate, allyl acrylate, ethylene glycol diacrylate, acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, hydroxypropyl methacrylate, etc.; the itaconic acid monoesters and diesters, such as the methyl, ethyl, allyl, dimethallyl, the maleic and fumaric acid monoesters, diesters and their amide and nitrile compounds, such as, ethyl allyl maleate, fumaryl dinitrile, dimethallyl fumarate, etc.; the ethers, such as methallyl allyl ether, vinyl allyl ether, vinyl methallyl ether, allyl crotyl ether, vinyl crotyl ether; cyanuric acid derivatives such as diallyl cyanurate, triallyl cyanurate, trivinyl cyanurate, or in general, triazine compounds having at least one polymerizable or copolymerizable unsaturated group attached directly or indirectly to the triazine ring, as well as the partial, soluble or fusible polymers of the hereinabove listed monomers, etc.

The modified unsaturated aliphatic alkyd resins of this invention can be used alone or with fillers, dyes, pigments, opacifiers, lubricants, plasticizers, natural and synthetic resins or other modifying bodies in, for example casting,

molding, laminating coating applications, and as adhesives, impregnants, and protective coatings.

In coating, impregnating and similar applications, the mixed monomeric or partially copolymerized materials, without added solvent can be applied to the object to be treated and polymerized, with or without the application of heat and pressure, to form the final insoluble polymeric composition in situ. These new synthetic materials can be used as impregnants for many porous bodies, such as cork, pottery, felts, or fabricated bodies with interstices, such as the windings of electrical coils, netted fibers, interwoven fibrous cotton or glass materials, etc. They can also be used for the production of wire coatings and winding tapes, and for protectively coating impervious articles, such as metals, or for coating and impregnating articles such as paper, Wood, cloth, glass fibers in felted, woven or other form, concrete, linoleum, synthetic boards, etc. These new synthetic materials can also be employed in making laminated fibrous sheet materials wherein superimposed layers of cloth, paper, glass fabrics or mats, etc., are firmly bonded together with these new compositions. Also, these new mixtures comprising at least one telomerized polyamide of this invention and at least one unsaturated aliphatic alkyd resin, with or without modifying agents, can be cast under pressure while being irradiated.

In preparing the interpolymerization products of the unsaturated aliphatic alkyd resin and the telomerized polyamide, the unsaturated alkyd resin can constitute as much as 98 or 99 percent by weight of the whole. In other cases the telomerized polyamide alone, or admixed with aliphatic comonomers or modifiers, can constitute as 98 to 99 percent by weight of the whole.

In general, the proportions of the components used in a particular formulation will depend upon the particular properties desired in the interpolymer. For most applications, it is preferred to use 30 to 90 percent of the unsaturated aliphatic alkyd resin and from 10 to 70 percent of the telomerized polyamide, since within these ranges interpolymers best adapted for most commercial applications can be produced.

Within these ranges the new interpolymers have a Wide range of properties. For example, depending upon the particular telomerized polyamide or mixture of telomerized polyamides used with the particular unsaturated aliphatic alkyd resin the particular proportions thereof, the conditions of polymerization, such as the temperature, pressure, presence or absence of additives, etc., the irradiation dose, and the extent of polymerization, they can vary in the degree of hardness, rigidity and resistance to solvents.

In the intermediate stages of copolymerization, some form fluid compositions of varying viscosities and may be so used. For coating or impregnating applications where the presence of a small amount of solvent in the cured composition is not objectionable, the mixed starting component can be diluted with volatile or non-volatile solvents or diluents best suited for the particular service application, and then can be polymerized after the application of the solution to the particular article to be coated or impregnated, or impregnated and coated. By suitable selection of the starting material and the conditions of the interpolymerization, interpolymers can be obtained in an insoluble, infusible state practically resistant to the destructive effect of other chemical bodies, such as acids, bases, salts, solvents, swelling agents, and the like.

When it is desired to modify the properties of the polymers of the telomerized polyamides of this invention, this can be accomplished by copolymerizing a mixture comprising at least one telomerized polyamide with at least one copolymerizable unsaturated ethylenic, or acetylenic hydrocarbon, radical, more particularly, a

13 radical, such as vinyl, allyl, methallyl, vinylidene, etc., or with a copolymerizable compound containing a grouping, for example, as in vinylidene fluoride, vinylidene cyanide, vinyl propionate, maleic anhydride, or its esters and amides, methyl maleic anhydride, tetrafluoroethylene, etc.

Additional examples of copolymerizable comonomers are monomeric or partially polymerized vinyl esters, such as the acetate, propionate, etc.; vinyl ketones, methvinyl ketones, olefinic nitriles, such as acrylonitrile, methacrylonitrile, fumaryl nitrile, beta cyano ethylacrylate, acrylic and methacrylic esters, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, glycol dimethacrylate, allyl methacrylate, hydroxypropyl methacrylate, etc.; itaconic esters, for example, dimethyl itaconate, diethyl itaconate, diallyl itaconate; olefinic amides, for example, acrylamide, itaconamide, the maleic monoand di-amides, and the corresponding imides, etc.; the vinyl ethers, for example, vinyl butyl ether, vinyl isobutyl ether, vinyl cyclohexyl ether, the dienes, etc., for example, butadiene, isoprene, dimethyl butadiene, etc.

In preparing copolymers of the telomerized polyamides with other polymerizable comonomers such as methyl methacrylate, acrylonitrile, and the like, the telomerized polyamides can constitute as little as 0.1 percent by weight of the whole, whereas in other cases, the telomerized polyamides alone can constitute as much as 98 to 99 percent of the whole. As in the case of the copolymers with unsaturated aliphatic alkyd resins, the proportion of the components in a particular formulation will depend upon the particular comonomers used and the particular properties desired in the copolymer. The polymers and copolymers can be prepared most readily by ionizing radiation.

Various methods of practicing the invention are illustrated by the following examples. These examples are intended merely to illustrate the invention and not in any sense to limit the manner in which the invention can be practiced. The parts and percentages recited therein and all through the specification, unless specifically provided otherwise, refers to parts by weight and percentages 'by weight.

EXAMPLE I In a suitable apparatus equipped with a stirrer, reflux condenser, inert gas inlet, heating mantle, and thermostatic control for the reactor, are placed 12 parts of ethylene diamine and 39.2 parts of maleic acid anhydride. The apparatus is first deoxygenated by sweeping dry deoxygenated nitrogen through the apparatus and thereafter allowing a slow stream of nitrogen to pass through during the reaction. The mixture is heated to about 100 C. for about one hour to give a quantitative yield of HOOCCH CH CONHCH CH NHOCCH CH COOH Then 51.2 parts of glycidyl acrylate and 0.25 part of tbutyl catechol are added and the reaction continued for about two hours to give the telomerized oligomer:

This is a light-colored resinous product.

(b) When an equivalent amount of glycidyl methacrylate is substituted for the glycidyl acrylate the corresponding methacrylyl derivative is obtained.

() When an equivalent amount of glycidyl acetate is 5 substituted for the glycidyl acrylate the corresponding acetyl derivative is obtained.

EXAMPLE II The procedure of Example I is repeated ten times using respectively instead of the 39.2 parts of maleic acid anhydride;

(a) 46.4 parts of fumaric acid;

(b) 44.8 parts of itaconic acid anhydride;

(c) 44.8 parts of citraconic acid anhydride;

((1) 60.8 parts of LZ-tetrahydrophthalic acid anhydride;

(e) 68.0 parts of 1,4-tetrahydrophthalic acid;

(f) 52.8 parts of mesaconic acid;

(g) 45.6 parts of acetylene dicarboxylic acid;

(h) 50.4 parts of alpha-methyl itaconic acid anhydride;

and

(i) 91.2 parts of decenedioic acid;

and there are obtained the corresponding products in which the center OOCCH=CHCONHCH CH NHOCCH=CHCONH portion of the molecule is replaced respectively by:

(a') O OCCH=OHCONHCH CH NHOCCH=CHCOO O O C ("3 OHzCONHOHzCHzNHO C(IJCH CO O- CH2 CH2 OH=CH (g) -OOCCECCONHCH CH NHOCCECCOO- and (11' -OOC(CH2)4CH=CH(CH2)4CONHCH2 CH2NHOC(CH2)4CH=CH(CH2)4COO EXAMPLE 111 The procedure of Example I is repeated six times using respectively instead of the 12 parts of ethylene diamine:

(a) 14.8 parts of trimethylene diamine;

(b) 28.8 parts of hexamethylene diamine; (c) 34.4 parts of octamethylene diamine; (d) 40.0 parts of 2,9-diaminodecane; (e) 12.1 parts of ethanolamine;

(f) 17.8 parts of 4-amino-butano1-1;

OHFCHC OO CHzCH I OH and there are obtained respectively:

(0/) CHFOHCOO 01123311021200 CCH=CHC ONHwHmNHO o CH=CHCO 0 CH2 OH OHFGHCOOGmoH (1)) 0112 00000113011011200CCH=OHC0NH(CH2)5NHOCCH=CIICOOCH2 )11 CIIg=CHGOOCH2CH Oil (0) CHFCHGOOCI'IZCCHIOOCCH=CHCONII(CII2)BNHOCCH=CIIGOOCH2 HI CHz=ClICOOC1IzJII (m (d') CHz=CHCOOCHzCCHzOOCCH OHCONHCH(CIIz)sCHNHOCOlI=CHCOOCII HI CH CH3 CIIZ=CIICOOOH2( JII (0') CHz=CHCOOCH2CCHzOOCCII=CHCONH(C1I;);OOCGH=GHCOOCH H CI'IFCHCOOOHZCH (f') CH2=CHOOOCHzCCH OOCCH=OHCONH(CH )4OOCOH=CHCOOOH C )H CHFCHCOOCH CH 8H Similar results are also obtained with equivalent amounts hydride are used instead of 24 parts and 49 parts respecof 2,3-diarnino-butane, decamethylene diamine, 2,2-diethtively, and there is obtained (11') CI-I =CHO O O CHAIJHCH O O C CH=CH lO ONHCHQCH NHO C CH=CH110C ()0 CH 0.11 ClIz ClICOOOlI: Ir

yl-propane-diamine-1,3, diethylene triamine, 1,4-diaminocyclohexane, 1,2 diarninocyclohexane, 1,4 -bis(amin0- In a similar way by using 72 parts of ethylene diamine methyl) cyclohexane, etc. and 127.40 parts of maleic anhydride, there is obtained (b) CHFCHC O0 CHzOHCHzO 0 0 CH=CH[CONHCH2CH2NHO C CH=CHlrzC 0 0 CH )11 CH2=CHCOOCHz H EXAMPLE IV 4 With 84 par-ts of ethylene diamine and 147 parts of suc- To the reactor of Example I there is added 24 parts of Cinic anhydlide there is Oblflined (c) CHFCHCO o 011201101120 0 c CH=CHICONHCH2CH2NIIO c c1-I=oH]Ho 0 0 out H CH2=CIICOOCII2CII 0'11 ethylene diamine and 49 parts of maleic anhydride, and EXAMPLE VI the mixture reacted at 180 C. for six hours or until titration of a sample with 1 N sodium hydroxide shows that it is substantially A mixture of 512 parts of the product of Example I, 204 parts of acetic anhydride and 1 part of tributyl amine are refluxed in a nitrogen atmosphere for one hour. Then 50 the acetic acid by-product is removed by distillation under HOOC(CH2)2[CONHCH-CHNHOC(CH2)2] QCOOH a reduced pressure of 5 mm. and there remains in the re- Then there is added 25.6 parts of glycidyl acrylate and action flask 592 parts of the product (a) 011?:011000 omoomo 0 o GH=CHCONHCHQCHZNHO o GH=CHCO 0 CH2 OOCH; CHFCHCOOOHzH omoo When the above procedure is repeated with equivalent 0.25 parts of t-butyl catechol and the reaction continued amounts of the products of Examples II-V the corre for another two hours to give the polymer: sponding diaeetyl derivatives are obtained.

CHF-CHGO O CHzCHCHzO O C CH=CHCOLNHOHZCH NHO C CH CHC 01400112 H Y CHFCHCOOCHzCH 611 EXAMPLE VII EXAMIPLE V The procedure of Example VI is repeated except that instead of acetic anhydride there is used 252 parts of The procedure of Example IV is used except that 60 acrylic anhydride containing 1% of tributyl amine, and parts of ethylene diamine and 107.8 parts of maleic anthere is obtained (a) OH CHCOOCH CCHgOOCCH=CHCONHCHCH NHOGCH=OHCOOCH 00CCH=CH CH OHCOOCI-I H CI'I2:CIICCO 17 18 When the above procedure is repeated with equivalent EXAMPLE XI amounts of the products of Examples IIV the corresponding tetraacrylyl derivatives are obtained. The seven products of Example IX, (a') to (g') inclu- EXAMPLE VIII sive, are treated with acetic anhydride by the procedure of Example VI and there are obtained the acetyl deriva- By repeating the procedure of Examples VI and VII a tives of the general formula l (a) CHFC CO 0 CHzCHCHgO 0 C CH=CHC O [NHCHzCHzNHO C CH=CHC 0]];CHQ

OCCH3 CHFfiJCOOCHzCH CH3 $0 0 CH3 number of times using molar equivalents respectively of the appropriate anhydrides, namely, methacrylic, stearic, and when acrylic anhydride is used as the acrylating agent methoxy acetic, acrylic and butyric anhydrides, the correaccording to Example VII, there are obtained the respecsponding ester products are obtained. tive products (b) CH2=(IJ C O O CHzCHCHzO O C CH CHCO[NHCH2CH2NHO C CH=CHCO],.CH7 CH3 OOCCH=CH2 CHFOHOOCH2 l H CHFOHCOO EXAMPLE IX 'th the values of 11 corresponding in each case to those To the reactor of Example I there are added, In a num- W1 ber of respective experiments, appropriate proportions of g; iz g Where n has the Ongmal numencal value ethylene diamine and maleic anhydride and reacted at or EXAMPLE XII 180 C. for six hours to give a series of products having the general formula When in Example IX other unsaturated aliphatic di- HOOCCH CHCO[NHCH CH2 carboxylic acids, such as itaconic, citraconic, mesaconic,

1,2-tetrahydrophthalic, etc., are used instead of maleic NHOccH CHCO]oH anhydride, the corresponding hydroxy-substituted diacrylwherein n equals 1, 3, 5, 10, 12, 14 and 15. These are yl terminated polyamides are obtained. These hydroxyin turn each reacted with two molar proportions of substituted polyamides are readily acrylated by the proceglycidyl methacrylate to give seven products respectively dures of VI, VII and VIII. of the general formula CH3 0H2= 3oo0oH2(lJHCH20OOCH=CHCO NHOHZOH2NHOOGH=OHCO],,CH2 OH OH2=(|3COOCH2(|JH CH3 0H where n=1 for Sample EXAMPLE XIII 11:3 for sample (b') The procedure of Example IX is repeated a number of n=5 for sample (c') times using equivalent quantities of an aromatic dicar- 11:10 for sample (d) boxylic acid, phthalic anhydride, instead of the aliphatic 11:12 for Sample (e) dicarboxylic succinic anhydride, and there is obtained a 21:14 for sample (f) series of products of the general formula n=15 for sample (g') OH2=O000oHicrroHzoloccfiHlooNHoHicfizNmnocoufliooooHz CH3 H onFooooomoH CH3 OH EXAMPLE X n=1 in sample (a') The procedure of Example IX is repeated a number of 11:5 in sample (b') times using molar equivalents of glycidyl acrylate instead :10 i Sample of glycidyl methacrylate, and there are obtained seven 12i 1 (d) products of the general formula CHFCHCHzC O O CHQCHCHsO O C CH=OHC ()[NHCH2CH2NHO C CH=CHC 0].,CH2

where n=1 for sample (a') EXAMPLE XIV n=3 for sample (b') :5 f sample The procedure of Example IX is repeated using equiva- :1() fo sample (d) lent quantities of an aromatic diamine p-xylylidene dia- =12 for sample (e) mine, NH CH C H CH NH instead of ethylene diamine, 14 fo Sample (f') and there is obtained a series of products of the general 11:15 for sample (g') formula I OH O CO 0 CHzCHCHzO O CCH=CHCO [NHCHzCoH4CH2NHO COH=CHCOLOH H CHz=CCOOCH2(]3H H: OH

1 9 in which 11:1 in sample (a') n: in sample (b') 11:10 in sample (c) 11:15 in sample (d') EXAMPLE XV The telomerized hydroxy-substituted polyamides of Example I, II and the acyl-substituted polyamide of Example VI are irradiated in an aluminum dish while exposed to air and they crosslink at 2.0, 2.1 and 2.0 megarads respectively.

The telomerized diacrylyl polyamides of Example VIII are similarly irradiated; they become insoluble and infusible at dosages in the range of 2.2 to 3.1 megarads.

' EXAMPLE XVI The tetraacrylyl-substituted polyamides of Examples VII and VIII are irradiated in an open container. These crosslink at irradiation dosages within the range of 0.90 to 1.4 megarads, indicating the extra sensitivity introduced into the diacrylyl telomerized polyamide by the introduction of two additional acrylyl groups.

EXAMPLE XVII The seven telomerized polyamides of Example IX are subjected to irradiation. Those having values of n from 1 to 14 crosslink under dosages increasing from 2 megarads for 11:1 to 4.6 megarads for n:14. For 12:15, crosslinking occurs at 6.7 megarads, indicating an economical upper limit for values of n being less. than 15. When however, an average value of less than 15 can be obtained by mixtures of polyamides of '11 being smaller than 15, for example n:1 to 12 with a polyamide of 11:15, for example equal mixtures of amides of 11:15 with amides of 11:1 and 5 respectively, crosslinking occurs at 3.1 and 4.2 megarads respectively.

Irradiation of the telomerized samples X(a) to X(g) and XI(a) inclusive shows similar results, indicating that 11:14 is an economical upper limit.

EXAMPLE XVIII The seven tetraacrylyl polyamides of Example XI(b) are submitted to irradiation of the linear accelerator and all of them crosslink in the range of 1 to 3.2 megarads indicating the marked effect of the additional acrylyl groups which not only lowers the dosage requirements but also raises the upper limit of the value of n. The r products vary from hard, tough, insoluble, infusible solids at 11:1 to tough, infusible, insoluble, progressively more elastic polymers at 11:15.

EXAMPLE XIX EXAMPLE XX A printed face sheet whose design corresponds to that of a wood grain is impregnated with a mixture of the telomerized polyamide, (1) IX(a'), 50 parts; (2) IX(c), parts; (3) IX(d), 10 parts; and (4) XI(b) where 11:2, 5 parts, and alkyd resin G, 15 parts; so that the sheet consists of 60 parts of polyamide mixture and parts of sheet by weight. This impregnated sheet is laid over a woodchip board and the whole irradiated to 4 megarads. There is obtained a finished board having the appearance of a fine grain, high gloss, varnished wood which is resistant to water, alcohol, acetone and most 0f the common organic solvents.

20 EXAMPLE XXI Parts Alkyd resin A 80 Telomerized polyamide Example III 20 The alkyd resin A and the telomerized polyamide are thoroughly and uniformly mixed and subjected to ionizing radiation and converted to an insoluble, infusible hard product at a dose of 3.6 megarads.

Fillers such as wood flour, alpha cellulose, shredded cellulose derivatives, asbestos, paper, cloth, sand, silica, calcium sulfate, etc., can be coated or impregnated with the mixture and the mass hardened by irradiation to produce formed articles of good appearance and excellent physical properties and improved heatresistance.

To improve the heat-resistance further the foregoing procedure is modified using a higher ratio of telomerized polyamide to the unsaturated alkyd as follows:

Parts Alkyd resin A 50 Telomerized polyamide VI 50 and Alkyd resin A Telomerized polyamide VI 25 Compositions of the kind illustrated in this example have the advantage that they do not contain radical initiators and can be stored for long periods of time, and still are readily cured without the addition of catalyst by the simple expedient of subjecting them to irradiation.

EXAMPLE XXII The procedure of Example XXI is repeated except that instead of Alkyd resin A, there is used Alkyd resin B and infusibility and insolubility is obtained at 3-4 megarads of irradiation.

The compositions of Example XXI and XXII can be used at room temperature, low pressure laminating resins for the preparation of reinforced laminates from glass mats or fabrics.

It will be understood of course that this invention is not limited to the interpolymerization of Alkyd resins A and B with the telomerized polyamide of Example VI, and that another acrylyl telomerized polyamide alone or in combination can be used, for example, the telomerized polyamides of Examples 1, II and VII-XII inclusive, can

. also be used.

In contrast, when the aromatic containing telomerized polyamides of Examples XIII and XIV are used, irradiation doses in excess of 18 megarads are required to produce hard, infusible polymers.

Similarly, high irradiation doses in excess of 16 megarads are required when the aromatic containing alkyd resin 1 is used with the acrylyl telomerized polyamides in contrast to the use of alkyd resins C, D, E, F, H and I which become infusible and insoluble in the range of 3.8 to 4.0 megarads.

The use of unsaturated alkyd resin G, which is an acrylyl terminated unsaturated alkyd in admixtures with the acrylyl telomerized aliphatic type polyamides, for example, the polyamides of Example I, II, and VI are particularly beneficial since in all cases erosslinking occurs within the range of 1.8 to 2.1 megarads.

EXAMPLE XXIII A smoothly sanded pineboard 12 inches long by 36 inches and %-inch thick is coated on one surface with a mixture of equal parts of the polyamides of Example XI to produce a layer of polyamide 0.005-inch in thickness, and the board is progressed under the sweeping beam of the linear accelerator to be given a uniform dose of 3 megarads. The finished board has the appearance of a high glass varnished lumber.

EXAMPLE XXIV Fifty parts of the telomerized polyamide of Example XI(a) is diluted with parts of glycol dimethacrylate and a concrete panel As-inch thick is impregnated with this solution and the panel irradiated to a dosage of 3.5 megarads; a Water-impervious panel is obtained.

EXAMPLE XXV A mixture of 80 parts of exploded wood fibers of the type used to prepare fiber board, 12 parts of the telomerized polyamide of Example XIII(b), 1 part of zinc stearate and seven parts of linseed oil are milled to uniformity, pressed into a board and given 4.8 megarads of irradiation. There is obtained a well knit hard board which is readily paintable with either solvent-type paints, or aqueous emulsion paints.

EXAMPLE XXVI Four parts of the polymer of Example IX(e') are added to 10 parts of water containing 0.5% of sodium dioctyl sulfosuccinate as an emulsifying agent and the mixture emulsified in a colloidal mill. The emulsion of the telomerized polyamide is added to 50 parts of prepuffed polystyrene beads mixed and the mixture tumbled until all the beads are uniformly coated. The water is then allowed to evaporate from the coated foamed beads which ad here slightly to each other. The coated foamed beads are then placed in a container such as a card-board box and irradiated to a dose of about 4 megarads. By this process there is obtained a foamed structure in which the beads are all bonded with infusible bonds to each other, the shape of which conforms to the form of the container.

EXAMPLE XXVII A uniform mixture of 40 parts of the diacrylyl polyamide of Example IX(a) and 60 parts of a plastisol grade of polyvinylchloride having a molecular weight of about 22 and Parts Nylon 66 75 Telomerized polyamide 25 Compositions of the kind illustrated in this example have the advantage that they do not contain radical initiators and can be stored for long periods of time, and still are readily cured without the addition of catalyst by the simple expedient of subjecting them to irradiation. The foregoing procedure is repeated with similar results using as the diacrylyl polyamide the respective telomerized polyamides of Examples I-IV and V-XII.

EXAMPLE XXIX The procedure of Example XXVII is repeated except that instead of nylon 66, there is used polycaprolactamide, and infusibility and insolubility is obtained at 3-4 megarads of irradiation.

In contrast, when the aromatic containing telomerized polyamides of Examples XIII and XIV and the acetyl telomerized polyamide of Example I(c) are used in EX- amples XXVII and XXVIII irradiation doses in excess of 18 megarads are required to produce hard infusible polymers.

Other methods of combining or mixing the polyamide resins and the diacrylyl polyamides can be used. For example the polyamide resin and the telomerized polyamide can be dissolved in a mutual solvent, such as dimethylformamide and other solvents well known for nylon, and films laid therefrom which can be subsequently radiated.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention to the exact details shown above except as they are defined in the following claims.

The invention claimed is:

1. The highly radiation-sensitive telomerized diacrylyl polyamide having the formula l l CHz=CCOOCHZCHCHQOOCRCOlARAOCRCOhO CH2(3HCH2000C=CH2 25,000 is prepared. This is melt-extruded into pipe and given an irradiation dose of 3 megarads. The polyvinylchloride is not degraded by this small dosage and the treatment makes the pipe insoluble and infusible so that it withstands hot water 210 F. and hot saturated brine at 215 F. without softening. It also withstands hot solutions of acetic acid, toluene, carbon tetrachloride, etc.

EXAMPLE XXVIII Parts Nylon 66 80 70 Telomerized polyamide 20 OX OX Wherein n has a value of 1-14;

A is a divalent radical selected from the class consisting of O- and NH, there being at least one said NH radical per polyamide molecule;

R represents a connecting linkage between two adjacent carboxylic radicals selected from the class consisting of a single valence bond and a divalent aliphatic hydrocarbon radical having 2-10 carbon atoms, at least of which R groups per polyamide molecule are unsaturated;

R is a divalent aliphatic hydrocarbon radical having 2-10 carbon atoms;

R" is a radical selected from the class consisting of hydrogen and methyl;

R" is a radical selected from the class consisting of hydrogen and aliphatic hydrocarbon radical having 1-18 carbon atoms; and

X is a radical selected from the class consisting of hydrogen and an acyl radical of the formula R"CO.

2. The telomerized diacrylyl polyamide of claim 1,

which has the formula CH2=CHCOOCH2?HCHzOOCCH=CHCONHCH2CH NHOCCH= CHCOO OH 23 24 3. The telomerized diacrylyl pclyamide of claim 1, 8. The process of claim 7 in which said diacrylyl polywhich has the formula amide is in intimate admixture with a polyamide resin CH2=CHCOOCH2CHCH2OOCCII= CHCONIICH2CIIzNHOCCH= (311000 01-12 l OOCCH=CH2 CIIg=CHCOOCH2C II CHz=CHCOC 4. The telomerized diacrylyl polyamide of claim 1, consisting essentially of a plurality of repeating units which has the formula having a formula selected from the class consisting of CHQ=CHCOO CI'IZEHICHZOO CC CIICOINIICI'IJCI'I2NI'IO CC CHCOIHOEJIL on 011 on! I GHz=CHCOOCHeCH ()H 5. The telomerized diacrylyl polyamide of claim 1, -R""CONH and -R""NHOCR""CONH wherewhich has the formula in R"" is a divalent saturated aliphatic hydrocarbon CHz -CHCOOCHzCHCH OOCCHCHCO[NHCHgCH NI-IOCCHCHCO],,OCH

on CH CH O 2 CH CH=CH cH--ofi OI-IFCHCOOCHHIIII 11 6. The telomerized diacrylyl polyamide of claim 1, 25 radical of 4-8 carbon atoms having at least 4 carbon which has the formula atoms in the linear chain between the two valencies and CH2=CIICOOCH CHCIIaOOCG=CHCO[NIIOH2CH2NHOCO=GHCO],,0CH

( 311 (3H3 Ha I CH2=CHCOOOHQCH on 7. A process for producing an improved polyamide having a molecular weight of at least 500, said polyamide resin composition comprising the treatment with at least resin comprising 10-70 percent by weight of the resultabout 0.5 megarad and no more than about 10 megarads ant mixture and said diacrylyl polyamide comprising of high energy, ionizing radiation equivalent to at least 30-90 percent by weight of the resultant mixture.

100,000-electron volts, of a highly radiation-sensitive 9. The process of claim 7 in which said diacrylyl polytelornerized diacrylyl polyamide having the formula amide is intimately admixed with a copolymcrizable R If on =t lcooomonomoGGRCOMR'AOCRCOLDCH OHCH OCC=CH wherein 4? monomer, said diacrylyl polyamide comprising 1-99 pern has avalue of 1-14; cent by weight of said copolymerizable mass and said A is a divalent radical selected from the class c0ns1stcopolymerizable monomer comprising 99-1 percent by ing of O- and -NH, there being at least one weight of said copolymerizable mass. said NH radical per polyamide molecule; 10. The process of claim 7 in which said diacrylyl R represents a divalent saturated aliphatic hydrocarbon radical having 2-10 carbon atoms, at least 75% of polyamide is in intimate admixture with an unsaturated aliphatic alkyd resin, said diacrylyl polyamide comprissaid R groups per polyamide molecule being uning 10-70 percent by weight of said copolymerizable t t d; mass and said unsaturated aliphatic alkyd resin com- R' is a divalent saturated aliphatic hydrocarbon radical prising about 30-90 percent by weight of said copolyhaving 2-10 carbon atoms; Fr merizable mass. R" is a radical selected from the class consisting of 11. The process of claim 7 in which said diacrylyl hydrogen and methyl; polyamide has the formula OH -CHC-QOOH CI-ICHQOOCCH=ClICONHCHzCHzNHOCCH=CHOOOCH:

H CH2=CHCOOCH2CH R"" is a radical selected from the class consisting of hydrogen and aliphatic hydrocarbon radical having 12. The process of claim 7 in which said diacrylyl 1-18 carbon atoms; and polyamide has the formula CH2=OIICOOCH2CHOH2OOGCH=CHCONHCH2CH2NHOCCH=CHCOOCH OOCCH=CH2 CHFCHCOOCHZJIH CH2=CHCO X is a radical selected from the class consisting of 70 13. The process of claim 7 in which said diacrylyl hydrogen and an acyl radical of the formula R""CO. polyamide has the formula C-HFCHCO OCH CHOHgOOCCH=CHCO[NHCHgCHgNI-IO 0CH=OH00],,O cm

14. The process of claim 7 in which said diacrylyl polyamide has the formula C HFCHCO O CHzCHCHzO O C C CHO O[NHCH CH NHO O O CHCOhO Oli (in his (lat CHz=CHC O O CHzCI-I 6H 10 radiation-sensitive telomerized diacrylyl polyamide havin g the formula:

R RI! l 0112 0000CHzfiJHCHzOCCRCOLAR/AOCRCOLOCHZCHCHZOCJJ=CHZ OX 0X wherein n has a value of ll4; 15. The process of claim 6 in which said diacrylyl A is a divalent radical selected from the class conpolyamide has the formula sisting of O and NH, there being at least one said NH radical per polyarnide molecule; R represents a divalent saturated aliphatic hydrocar- CH2=CHCOOCHQCHOHQOOCCH-CH-CO[NHCH2OH2NHOCCHCHC0],,O0H2

OH 0 2 CH2 C 2 CH2 EH=6H EH41;

CH2=CHCOOCH2CH bon radical having 210 carbon atoms, at least 75 percent of said R groups per polyamide molecule being unsaturated;

16. A radiated polymeric product produced according R is a divalent saturated aliphatic hydrocarbon radito the Process of claim cal havingZ-lO carbon atoms;

17. A radiated polymeric product produced according R g z z g g g from the Class conslstmg of to the Process of Clalm R" is a radical selected from the class consisting of 18. A radiated polymeric product produced acco hydrogen and aliphatic hydrocarbon radical having ing to the process of claim 9. 148 carbm atoms; and

p 40 X is a radical selected from the class consisting of hyto 35:3 iggf ig product produced accordmg drogen and an acyl radical of the formula R""CO.

20. A radiated polymeric product produced accord- References Cited ing to the process of claim 11. UNITED STATES PATENTS 21. A radiated polymeric product produced a d- G y ing to the p c ss of c a 1 2,251,946 8/1941 Lott 260-561 22. A radiated polymeric product produced according to the process of Claim MURRAY TILLMAN, Prlmary Examiner 23. A radiated polymeric product produced according RICHARD TURER, Assistant Examiner to the process of claim 14. US Cl. XR.

24. A process for producing an improved polyamide resin composition comprising the treatment with at least 6 2 g 7 g itsg g gdl ifi l about 0.5 megarad of high energy, ionizing radiation equivalent to at least 100,000 electron volts, of a highly mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,483,105 Dated December 9, 1969 Inventor(s) GaetanO F. D'Alelio It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

in the CaQtiOn after 'PPG Industries, Inc." insert --Pittsburgh,Pennsylvani.

Column 3 line 1 "Telemerized" should be --Telomerized--;

Columns 3 and 4 first line of formula "COCl" should read COCl--:

Column 3, line 56I last line of formula "OOCRR" should be --OOCR' ----7 Column 4, line 2g, last line of formula (Eq. 3) should be --(Eq. 4) ---7 Column 14 line 17 (d) 1.2" should read --(d) l,2--;

Column 17, line 14, after "methoxy acetic" insert --acetic,---

Column 18, line 53 insert --in which-- before n-l in sample (a') SIGNED ANY) SEALED AUG 181970 sh x. m.

. Winner of Patents 

